This invention relates to methods of encapsulating solid state electronic devices and the encapsulated devices. More specifically, this invention relates to encapsulated organic polymeric light emitting devices. Principally this invention describes encapsulating such devices to prevent ambient moisture and oxygen from reacting with materials used in the fabrication of the devices.
Diodes and particularly light emitting diodes (LED""s) fabricated with conjugated organic polymer layers have attracted attention due to their potential for use in display technology [J. H. Burroughs, D. D. C. Bradley, A. R. Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, and A. B. Holmes, Nature 347, 539 (1990); D. Braun and A. J. Heeger, Appl. Phys. Lett. 58, 1982 (1991)]. These references as well as all additional articles, patents and patent applications referenced herein are incorporated by reference. Among the promising materials for use as active layers in polymer LED""s are poly (phenylene vinylene), (xe2x80x9cPPVxe2x80x9d), and soluble derivatives of PPV such as, for example, poly(2-methyoxy-5-(2xe2x80x2-ethylhexyloxy)-1,4-phenylene vinylene), (xe2x80x9cMEH-PPVxe2x80x9d), a semiconducting polymer with an energy gap Eg of≈2.1 eV. This material is described in more detail in U.S. Pat. No. 5,189,136. Another material described as useful in this application is poly(2,5-bis(cholestanoxy)-1,4-phenylene vinylene), (xe2x80x9cBCHA-PPVxe2x80x9d), a semiconducting polymer with an energy gap Eg of≈2.2 eV. This material is described in more detail in U.S. patent application Ser. No. 07/800,555. Other suitable polymers include, for example; OCIC10-PPV; the poly(3-alkylthiophenes) as described by D. Braun, G. Gustafsson, D. McBranch and A. J. Heeger, J. Appl. Phys. 72, 564 (1992) and related derivatives as described by M. Berggren, O. Inganas, G. Gustafsson, J. Rasmusson, M. R. Andersson, T. Hjertberg and O. Wennerstrom; poly(paraphenylene as described by G. Grem, G. Leditzky, B. Ullrich, and G. Leising, Adv. Mater. 4, 36 (1992), and its soluble derivatives as described by Z. Yang, I. Sokolik, F. E. Karasz in Macromolecules, 26, 1188 (1993), polyquinoline as described by I. D. Parker J. Appl. Phys, Appl. Phys. Lett. 65, 1272 (1994). Blends of conjugated semiconducting polymers in non-conjugated host polymers are also useful as the active layers in polymer LED""s as described by C. Zhang, H. von Seggern, K. Pakbaz, B. Kraabel, H.-W. Schmidt and A. J. Heeger, Synth. Met., 62, 35 (1994). Also useful are blends comprising two or more conjugated polymers as described by H. Nishino, G. Yu, T-A Chen, R. D. Rieke and A. J. Heeger, Synth. Met., 48, 243 (1995) Generally, materials for use as active layers in polymer LED""s include semiconducting conjugated polymers, more specifically semiconducting conjugated polymers which exhibit photoluminescence, and still more specifically semiconducting conjugated polymers which exhibit photoluminescence and which are soluble and processible from solution into uniform thin films.
In the field of organic polymer-based LED""s it has been taught in the art to employ a relatively high work function metal as the anode; said high work function anode serving to inject holes into the otherwise filled xcfx80-band of the semiconducting, luminescent polymer. Relatively low work function metals are preferred as the cathode material; said low work function cathode serving to inject electrons into the otherwise empty xcfx80*-band of the semiconducting, luminescent polymer. The holes injected at the anode and the electrons injected at the cathode recombine radiatively within the active layer and light is emitted. The criteria for suitable electrodes are described in detail by I. D. Parker, J. Appl. Phys, 75, 1656 (1994).
Suitable relatively high work function metals for use as anode materials are transparent conducting thin films of indium/tin-oxide [H. Burroughs, D. D. C. Bradley, A. R.- Brown, R. N. Marks, K. Mackay, R. H. Friend, P. L. Burns, and A. B. Holmes, Nature 347, 539 (1990); D. Braun and A. J. Heeger, Appl. Phys. Lett. 58, 1982 (1991)]. Alternatively, thin films of conducting polymers such as poly(aniline), (xe2x80x9cPANIxe2x80x9d) can be used as demonstrated by G. Gustafsson, Y. Cao, G. M. Treacy, F. Klavetter, N. Colaneri, and A. J. Heeger, Nature, 357, 477 (1992), by Y. Yang and A. J. Heeger, Appl. Phys. Lett 64, 1245 (1994) and U.S. patent application Ser. No. 08/205,519, by Y. Yang, E. Westerweele, C. Zhang, P. Smith and A. J. Heeger, J. Appl. Phys. 77, 694 (1995), by J. Gao, A. J. Heeger, J. Y Lee and C. Y Kim, Synth. Met., 82,221 (1996) and by Y. Cao, G. Yu, C Zhang, R. Menon and A. J. Heeger, Appl. Phys. Lett. 70, 3191, (1997). Thin films of indium/tin-oxide and thin films of polyaniline in the conducting emeraldine salt form are preferred because, as transparent electrodes, both enable the emitted light from the LED to radiate from the device in useful levels.
Suitable relatively low work function metals for use as cathode materials are the alkaline earth metals such as calcium, barium, strontium and rare earth metals such as ytterbium. Alloys of low work function metals, such as for example alloys of magnesium in silver and alloys of lithium in aluminum, are also known in prior art (U.S. Pat. Nos. 5,047,687; 5,059,862 and 5,408,109). The thickness of the electron injection cathode layer has ranged from 200-5000 xc3x85 as demonstrated in the prior art (U.S. Pat. No. 5,151,629, U.S. Pat. No. 5,247,190, U.S. Pat. No. 5,317,169 and J. Kido, H. Shionoya, K. Nagai, Appl. Phys. Lett., 67(1995)2281). A lower limit of 200-500 Angstrom units (xc3x85) is required in order to form a continuous film (full coverage) for cathode layer (U.S. Pat. No. 5,512,654; J. C. Scott, J. H. Kaufman, P. J. Brock, R. DiPietro, J. Salem and J. A. Goitia, J. Appl. Phys., 79(1996)2745; I. D. Parker, H. H. Kim, Appl. Phys. Lett., 64(1994)1774). In addition to good coverage, thicker cathode layers were believed to provide self-encapsulation to keep oxygen and water vapor away from the chemically active parts of the device.
Electron-injecting cathodes comprising ultra-thin layer alkaline earth metals, calcium, strontium and barium, have been described for polymer light emitting diodes with high brightness and high efficiency. Compared to conventional cathodes fabricated from the same metals (and other low work function metals) as films with thickness greater than 200 xc3x85, cathodes comprising ultra-thin layer alkaline earth metals with thicknesses less than 100 xc3x85 (e.g., 15 xc3x85 to 100 xc3x85) provide significant improvements in stability and operating life to polymer light emitting diodes [Y. Cao and G.Yu, U.S. patent application Ser. No. 08/872,657.
Unfortunately, although the use of low work function electrodes is required for efficient injection of electrons from the cathode and for satisfactory device performance, low work function metals such as calcium, barium and strontium are typically unstable and readily react with oxygen and/or water vapor at room temperature and even more vigorously at elevated temperatures.
Despite the improvements in the construction of polymer LED""s, a persistent problem has been fast decay of the device efficiency (and light output) during storage and during stress, especially at elevated temperature. Thus, there is a need for methods of encapsulation of such devices, said encapsulation being sufficient to prevent water vapor and oxygen from diffusing into the device and thereby limiting the useful lifetime.
Light-emitting devices fabricated with organic polymeric materials as the active layers typically comprise reactive low work function metals such as, for example, calcium, barium, or strontium. During normal use of these devices, moisture and to a lesser extent oxygen can come in contact with these metals and react to form hydroxides and/or oxides. Exposure to oxygen, particularly in the presence of light, can lead to photo-oxidative degradation of the luminescent semiconducting polymer as well. Such reactions will significantly reduce the performance of the light emitting properties of the devices. Prolonged exposure to ambient air leads to significant reduction in light output from devices. Often these reactions will lead to a complete elimination of the light emitting properties of these devices, rendering them useless as light sources. Many of the known processes for achieving a hermetic encapsulation of electronic devices require that the devices be heated to temperatures in excess of 300xc2x0 C. during the encapsulation process. Most polymer based light-emitting devices are not compatible with such high temperatures.
We have now found a technique for encapsulating polymeric light-emitting devices at the low method temperatures. The method of encapsulation provides a hermetic seal between the device and the ambient air with its harmful moisture and oxygen.
The method for encapsulation of this invention is one in which the overall thickness of the device is not significantly increased by the encapsulation of the device.
The method can, if desired, be carried out with fewer individual process steps than methods known to the art.
In accord with this invention the entire device is protected by depositing at low temperatures a thin film comprising an inorganic refractory material, such as a ceramic, for example silicon-nitride or silicon-oxide over the reactive cathodes present in the device structure. In a preferred embodiment, the deposit of the inorganic refractory material layer is preceded by depositing at low temperatures a thin film of a non-reactive metal, such as aluminum, over the reactive cathode metal. Following this layer, the thin film comprising an inorganic refractory material, such as a ceramic for example silicon-nitride or silicon-oxide is laid down, again at low temperatures. The two layer structure is preferred. When depositing these layers at low temperatures, such as below about 300xc2x0 C., they typically contain microscopic pinholes. If the single layer of metal were used alone as encapsulation, moisture and oxygen would be able to penetrate these pinholes and harm the performance of the device. However, because the probability of a pinhole occurring at exactly the same location in both layers is insignificant, the use of two layers, the non-reactive metal layer and then the refractory thin film, prevent moisture and oxygen from reaching the reactive materials in the device. This occurs even though the layers are deposited at temperatures below 100xc2x0 C.
In a preferred embodiment of the invention, the non-reactive metal layer is patterned in such a way as to form rows across the device. This geometry is often used to fabricate matrix displays by forming pixels at the intersections of rows and columns. In this embodiment the harmful moisture and oxygen can reach the reactive components of the device at the edge of the non-reactive metal rows. The subsequently-deposited ceramic film prevents moisture and oxygen from reaching the reactive metal in this embodiment of the invention.
In another preferred embodiment the non-reactive metal layer and ceramic thin film layer is followed by a thin lid secured by a frame of epoxy around the perimeter of the device. This lid offers additional protection from ambient moisture and oxygen. The lid can be fabricated from any material, which offers a sufficient barrier against moisture and oxygen. Some examples of lids are, plastics, glass, ceramics and other non-reactive metals.
In yet another preferred embodiment of the invention the lid is secured by dispersing epoxy over a substantial region such as the entire light-active area of the device.
In yet another preferred embodiment of the invention the ceramic thin film is patterned into a frame shape. A thin film metal is deposited on top of this ceramic frame and patterned into the same frame shape. An identically shaped metal thin film is deposited and patterned on the cover plate. The cover plate is attached to the ceramic thin film frame using metal solder. In this structure the solder and the ceramic thin film frame provide the sealing of the device.
In yet another preferred embodiment of the invention a ceramic thin film is deposited over the entire active area of the device. A thin film metal is deposited and patterned into a frame shape. A similar metal frame is formed on the cover lid. The cover plate is attached to the ceramic thin film frame using metal solder.